JPH02174938A - Hydrocarbon oil conversion process and catalyst for use in said process - Google Patents

Abstract

PURPOSE: To perform the conversion of a high b.p. fraction with high selectivity by containing a group VI and/or a group VIII metals in a catalyst for the hydrocracking of a hydrocarbon oil and containing a zeolite Y particle having average crystallite size and a binder. CONSTITUTION: The hydrocarbon oil is converted to a product having low average molecular weight and low average b.p. by allowing to contact with a hydrocracking catalyst in the presence of hydrogen at high temp. and high pressure. In such a case, the catalyst contains a hydrogenation component of the group VI and/or the group VIII metals such as Ni and Pt, the zeolite Y particles having an average crystallite size of less than 0.7 μm and the binder such as silica or alumina. The catalyst exhibits selectivity to the conversion of the higher b.p. fraction of a hydrocarbon feeding raw material.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a method for converting hydrocarbon oils into products of lower average molecular weight and lower average boiling point in the presence of hydrogen, and zeolite Y particles used in the method. and on catalysts containing binders.

The present invention is particularly directed to overcoming the problem of increasing utilization of residual oils found in today's crude oil feedstocks.

′−・ Bi. From European Patent Specification No. 0216938, 20 to 70 zI4 of the particles have a diameter of 3 micrometers or less;
comprises a faujasite type Y zeolite having a particle size distribution such that t has a particle diameter of 3 to 12 micrometers and lO to 40Xwt of the particles have a particle diameter of 12 to 30 micrometers, and Catalysts for the hydrotreatment of heavy hydrocarbon oils are known which also contain metal components selected from the VfA group and the II group.

This publication states that if the particle size distribution deviates from the above range, the catalytic activity decreases.

. However, unexpectedly, it contains zeolite Y particles and a binder, and the zeolite Y particles have an average crystallite size of less than 0.7 micrometers.
It has been found that catalysts having the same size exhibit improved selectivity for the conversion of higher boiling fractions of hydrocarbon feedstocks.

Accordingly, the present invention is a process for converting hydrocarbon oils into products of lower average molecular weight and lower average boiling point, the process comprising converting hydrocarbon oils into water in the presence of hydrogen at elevated temperature and pressure. contact with an addition-cracking catalyst, the catalyst containing at least one
The conversion process comprises a hydrogenation component of a group metal and/or a group I metal, zeolite Y particles and a binder, the zeolite Y particles having an average crystallite size of less than 0.7 micrometers.

The present invention also comprises zeolite Y particles and a binder and at least one group I metal and/or group II metal hydrogenation component, the zeolite Y particles having an average crystallite size of less than 0.7 micrometers. Regarding the composition.

The process according to the invention is particularly suitable for hydrogenolysis. The products of lower average molecular weight and lower average boiling point obtained in this process include gaseous substances, generally C4-4 hydrocarbons, naphtha and middle distillate fractions, ie soluble oil fractions and gas oil fractions.

The crystallite size of the zeolite Y particles was measured by a conventional method using scanning electron micrograph (SEM) analysis. If the particles used are spheres, the term "crystalline size" of course refers to their diameter. Further information on this crystallite size measurement method can be found, for example, in E, G, Derouar+e.

S, DemIlletrie + Z, Gabelie
a and N, Blom t 8 ppl.

Catal, 1 (1981) 201.

If agglomerations and/or alternations were present in zeolite 7 grains-f-, the dimensions of the particles forming these agglomerations or alternations were measured.

Particles suitable for use in the lying method are smaller than 20.7 micrometers, preferably between 0.01 and 0.7 micrometers.
in the range of 5 micrometers, more preferably in the range of 0.05 to 0.3 micrometers, more preferably 0.
．． It has an average crystallite size ranging from 2 to 0.3 micrometers. The distribution of crystallite size also affects the performance of the catalyst particles, and at least 80% of the particles are between 0.1 and 0.
．． more preferably at least 90% of the particles have a crystallite size of 4 micrometers to 1 cm, and more preferably at least 90% of the particles are between 0.2 and 0.3
Crystallite size distributions having crystallite sizes in the micrometer range are suitable for use in the present method.

The particle size of the catalyst particles can vary over a wide range. A suitable range of average catalyst particle size is 0.8 to 5.0 millimeters.

The catalyst used in this method includes zeolite Y particles. Zeolite Y that can be used includes ultrastable zeolite Y, rare earth exchanged zeolite Y, and mixtures thereof. The unit cell size of zeolite i-Y is suitably 24.19 to 24.60, preferably 24.19 to 24.
．． 45 people, more preferably 24, 19 to 24.3 people
There are 5 people. Such low unit cell dimensions are favorable for the performance of hydrocracking catalysts used with feedstocks having a relatively high proportion of high-boiling hydrocarbons, as described in European Patent Specification No. 024.1678. It has been known.

Zeolite hY is characterized by a bojasite X-ray diffraction image. Sin,/l/220. :IE:)I
Zeolite Y having an i ratio of 4 to 25, more preferably 8 to 15 is preferred.

The zeolite catalyst used in the process according to the invention suitably has an amount of zeolite Y ranging from 20 to 90Xwt and an amount of binder ranging from 10 to 80Xwt, based on the total amount of zeolite Y and binder. . In particular, the catalyst contains zeolite Y in an amount ranging from 60 to 85% and binder in an amount ranging from 15 to 40%, based on the total amount of zeolite and binder. Particularly suitable catalyst compositions are described in European Patent Specification No. 0247678.

The zeolite is combined with a Group I and/or Group II metal hydrogenation component. This attachment may be performed by any method known in the art. Preferably this bonding is carried out by impregnation or co-mulling. In co-mulling, the zeolite is mixed in the presence of water with a hydrogenation component and optionally a binder to obtain an extrudable paste.

A description of co-mulling can be found in US Pat. No. 3,853,747.

The binder present in the catalyst suitably comprises an inorganic refractory oxide or a mixture thereof. Applicable for both amorphous and crystalline binders. Examples of suitable binders include silica, alumina, silica-alumina, chalk, zirconia, silica-zirconia, titania and silica-boria. Preferably, aluminum is used as the binder.

If mixtures are used, the choice is preferably made from alumina, silica-alumina and titania. The silica-alumina acts not only as a binder but also as a cranking component.

The hydrogenation component on the catalyst is selected from metals of Groups ■ and ■ of the Periodic Table of the Elements. Suitably the hydrogenation component is selected from the group consisting of molybdenum, tungsten, cobalt, nickel, palladium and platinum. Preferably catalysts containing nickel and tungsten are used.

The amount of hydrogenation component in the catalyst is suitably from 0.1 to 4, calculated as metal per 100 parts by weight (pbw) of total catalyst.
0 pbw of group metal component and 2 to 40 pbw of ■
Group metal components range. In particular, catalysts containing as hydrogenation component 0.5 to 10 pbw of group II metal component and 5 to 20 pbw of group II metal component, calculated as metal per 1100 pb of total catalyst, are suitable for use in the process according to the invention. The hydrogenation components in the catalyst can be in the oxide and/or sulfide state.

Hydrocarbon feedstocks that can be used in this process include tar oil, vacuum gas oil, deasphalted oil, atmospheric resid, vacuum resid, catalytic cracking cycle oil, pyrolysis gas oil, and optionally from resid upgrading processes or Includes synthetic crude oil derived from tar sands, shale oil or biomass. Combinations of various hydrocarbon oils may also be used.

Suitable process conditions for this process are temperatures in the range 250 to 500°C, hydrogen pressure up to 300 bar and 0.1 to 10 kg feed/liter catalyst/hour (kg/1-
h) includes the space velocity. 100 to 500ONj2/
A gas/feedstock ratio of kg feedstock may be suitably used.

Preferably, the hydroconversion process comprises 270 to 470
C., a pressure of 25 to 200 bar and a space velocity of 0.2 to 5 kg feedstock per liter of catalyst per hour. Preferably 250 to 200 ONf
A gas/feed ratio of /kg is applied.

The invention is illustrated by the following examples.

- Soil In this example, five catalysts are produced. Catalysts A, B and C are according to the invention.

Touch I~24, unit cell size of 33, sodium oxide content of 0.06Xwt, silica to alumina molar ratio of 8.8, loss on ignition of 25.6%-t and average of 0.3 micrometers Stabilized crystalline synthetic zeolite Y with microcrystalline size 806.5g ignition loss 2548%w
202.0 g of hydrated aluminum oxide.

To this mixture was added 311 g of a solution containing 95.3 g of HOs as ammonium metatungstate and 28.1 g of NiO as nickel nitrate. After kneading this mixture for 5 minutes, a mixture of 7.5 g of acetic acid and 262 g of water was added and kneading continued for 40 minutes. This mixture was then extruded into 1.7 mm extrudates. The extrudates were dried at 120°C for 2 hours and finally calcined at 500°C for 2 hours.

The weight ratio of zeolite Y to binder was 80/20 and the calcined extrudate had a weight ratio of 2,
It contained 6% wt Ni and 8.2% wt W.

Catalyst A was used to obtain particles with an average particle size of 0.3 mm (40-60 mesh, Tyler equivalent).
Catalyst B was obtained by crushing and sieving.

Hobutan 24, unit cell size of 34 people, average crystallite size of 0.3 micrometers, molar ratio of silica to alumina of 9.8, sodium oxide content of 0.065%-t and 18.4%- T intense heat? Ignition reduction of stabilized crystalline synthetic zeolite Y735.3g with JIiu! 25.8
%wt aluminum oxide hydride. To this mixture was added 311 g of a solution containing 95.3 g of ammonium metatungstate as ammonium metatungstate and 28.1 g of NiO as nickel nitrate.

After kneading this mixture for 5 minutes, 7.5 g of acetic acid and 262 g of water were mixed.
was added and mixing continued for 40 minutes. This mixture was then extruded into a 1.7 mm extrudate. The extrudates were dried at 120"C for 2 hours and finally calcined at 500"C for 2 hours.

The weight ratio of zeolite Y to binder was 80/20 and the calcined extrudate had a weight ratio of 2.
It contained 6%-t Ni and 8.2%-t W.

For school use, the unit cell size is 24, 33, sodium oxide content of 0.05% wt, silica to alumina molar ratio of 9.6, ignition loss of 12.5% and 1.0 micrometers. Ignite 685.7 grams of stabilized crystalline synthetic zeolite Y with average crystallite size 17J2ffi25
．． Mixed with 202.0 g of 8% wt hydrated aluminum oxide. To this mixture was added 311 g of a solution containing 95.3 g h'Oi as ammonium metatungstate and 28.1 g NtO as nickel nitrate. After kneading this mixture for 5 minutes, a mixture of 7.5 g of acetic acid and 262 g of water was added and kneading continued for 40 minutes. This mixture was then extruded into 1.7 m extrudates. The extrudates were dried at 120 °C for 2 hours and finally at 500 °C.
Roasted at 'C for 2 hours.

The weight ratio of zeolite Y to binder was 80/20 and the calcined extrudate had a weight ratio of 2.
It contained 6% Ni and 8.2% W.

Catalyst E was obtained by crushing and sieving the catalyst to obtain particles having an average particle size of 0.3 millimeters (40-60 mesh, Tyler equivalent).

±-''- The catalyst described in Example 1 was tested in a hydrocracking experiment using a hydrocarbon feedstock with the following properties: C (%-t)
:86.2 H(%Kat) :t3. .

d (70/4): 0.826 Viscosity (100°C): 4.87 cS (ASTM-D
-445) Viscosity (60'C): 12.43cS (
ASTM-D-445) RCT (%wt):
0.05 (^STM-D-542)! ,B,P
, (”C); 20510/20 (”C)
:332/37030/40(”C) :392
/41050/60(”C):42B/4487
0/80('C) :467/49290
('C): 525F, B, P, ('C)
The 859B catalyst was diluted with 0.2 m5ic particles in a 1:1 volume ratio. The catalyst was then presulfided. Hydrogenolysis was then carried out under the following operating conditions: WH3V: 1.1 kg-f
-',h-'H! S partial pressure: 1.4 bar Total pressure: 130 bar Gas/feedstock ratio: L 000 NJI! kg-' experiments were performed in single flow operation.

The performance of the catalyst measured was 300 DEG C. - the temperature required to achieve a 70 weight conversion of material. The results are shown in Table 1.

To demonstrate the utility of the process according to the invention for heavy hydrocarbon conversion, the conversion of hydrocarbons boiling above 300°C and the conversion of hydrocarbons boiling above 530'C are measured. These conversions are defined as follows: C300°C"i, -C300°C"C300°C"in and C530'C"t, -C530'c"outC530
℃"i, 1 where "i, II means entering the reactor, ou
t'' means coming out of the reactor, C300°C means the content of hydrocarbons boiling above 300°C, and 530°C means the content of hydrocarbons boiling above 530'C. do.

The ratio of these two conversions for catalysts A-E is also shown in Table 1.

It can be concluded that Experiment Nα Catalyst Table-1-1 ^. However, the selectivity is significantly improved using catalyst particles of the same size but containing particulate zeolite Y of smaller crystallite size.

Claims (17)

[Claims] (1) A method of converting a hydrocarbon oil to a product of lower average molecular weight and lower average boiling point, the process comprising contacting the hydrocarbon oil with a hydrogenolysis catalyst in the presence of hydrogen at elevated temperature and pressure. , the catalyst comprises at least one group VI metal and/or group VIII metal hydrogenation component and zeolite Y particles and a binder, the zeolite Y particles having 0.
said conversion method comprising having an average crystallite size of less than 7 micrometers. (2) The method of claim 1, wherein the zeolite Y particles have an average crystallite size in the range of 0.01 to 0.5 micrometers. (3) The method according to claim 1 or 2, wherein zeolite Y is selected from the group consisting of ultrastable zeolite Y, rare earth exchanged zeolite Y, and mixtures thereof. (4) Claim 1-- which uses zeolite Y having a unit cell size of 24.19 Å to 24.60 Å.
The method described in any of Section 3. (5) The method according to any one of claims 1 to 4, wherein a catalyst containing an inorganic refractory oxide is used as a binder. (6) Using as a binder a catalyst containing one or more compounds selected from the group consisting of silica, alumina, silica-alumina, chalk, zirconia, silica-zirconia, titania, silica-boria and mixtures thereof. A method according to claim 5. (7) Calculated as metal per 100 pbw of total catalyst: 0
．． Claims 1-6 using a catalyst comprising 1 to 40 parts by weight (pbw) of a group VIII metal hydrogenation component and/or 2 to 40 pbw of a group VI metal hydrogenation component
The method described in any of the paragraphs. (8) Claim 1-- which uses a catalyst containing one or more metals from the group consisting of nickel, cobalt, molybdenum, tungsten, platinum and palladium.
The method described in any of Section 7. (9) Conversion at temperatures of 250 to 500° C., hydrogen pressures of up to 300 bar, 0.0 ml of feedstock per liter of catalyst per hour.
9. A process according to any of claims 1 to 8, carried out at a space velocity of 1 to 10 kg and a H_2/feed ratio of 100 to 5000 Nl/kg. (10) A catalyst composition comprising zeolite Y particles and a binder and at least one Group VI metal and/or Group VIII metal hydrogenation component, wherein the zeolite Y particles have an average crystallite size of less than 0.7 micrometers. thing. (11) A catalyst composition according to claim 10, comprising zeolite Y particles having an average crystallite size in the range of 0.01 to 0.5 micrometers. (12) Ultra-stable zeolite Y, rare earth exchanged zeolite Y
The catalyst composition according to claim 10 or 11, comprising zeolite Y selected from the group consisting of zeolite Y and mixtures thereof. (13) Claim 1 comprising zeolite Y particles having a unit cell size of 24.19 Å to 24.60 Å
Catalyst composition according to any one of items 0-12. (14) The catalyst composition according to any one of claims 10 to 13, which contains an inorganic refractory oxide as a binder. (15) Claims containing as a binder one or more compounds selected from the group consisting of silica, alumina, silica-alumina, chalk, zirconia, silica-zirconia, titania, silica-boria, and mixtures thereof. 15. Catalyst composition according to item 14. (16) Claims 10-15 comprising 0.1 to 40 pbw of a group VIII metal hydrogenation component and/or 2 to 40 pbw of a group VI metal hydrogenation component calculated as metal per 100 pbw of total catalyst. A catalyst composition according to any one of the above. (17) The catalyst composition according to any one of claims 10 to 16, comprising one or more metals from the group consisting of nickel, cobalt, molybdenum, tungsten, platinum and palladium.